The invention relates to a process for the curing of surface coatings, whereby the surface hardness of the cured surface coating is increased by means of irradiation with UV light, and to a polymerisable composition.
In U.S. Pat. No. 4,121,985 the resistance of thermoplastic polyurethane surfaces to solvents and abrasion is improved by treatment of the surface with a mixture of solvent and photo-initiator and by subsequent irradiation with UV light. Derwent No. 94-252879/31 (JP-A Hei 6 184267) describes a polyurethane resin obtained by reacting polyol mixtures, containing chlorinated polyols and polyols having COOH groups, with polyisocyanates and unsaturated monohydroxy compounds and, where appropriate, a photoinitiator. DE-A 42 37 695 claims surface-coating compositions that contain functionalised resins having xcex1,xcex2-unsaturated groups and that are cured thermally. Derwent No. 87-331357 (JP-A Sho 62 236867) describes a curing process combining thermal and photochemical curing. Derwent No. 85-188037 (JP-A Sho 60 118271) discloses a combined heat- and UV-curable composition. EP-A 600 262 claims photoresist compositions having heat- and UV-curable components. In DE-A 33 32 004 and EP-A 247 563 there are prepared UV-curable surface-coating systems that comprise epoxide/amine- or polyol/isocyanate-based resins.
In the art there is a need for resins for coatings and surface coatings that exhibit good properties especially in respect of the durability of the cured surface.
It has now been found, surprisingly, that coatings having very good surface properties can be obtained by means of a process for the curing of a polymerisable composition comprising
(A) a coating system based on
(I) a polyacrylate polyol and/or polyester polyol with melamine or
(II) a polyacrylate polyol and/or polyester polyol with a blocked or unblocked polyisocyanate or
(III) a carboxyl-, anhydride- or amino-functional polyester and/or polyacrylate with an epoxy-functional polyester or polyacrylate, or
(IV) a mixture of (I), (II), (III) and/or (IV),
(B) an OHxe2x80x94, NH2xe2x80x94, COOHxe2x80x94, epoxy- or NCO-functional resin containing, in addition, at least one ethylenically unsaturated double bond, it being necessary for a spacer group of at least 4 linearly linked atoms to be present between the double bond and the functional group,
wherein components (A) and (B) do not contain halogen, and
(C) at least one photoinitiator,
by thermal treatment and, for the purpose of improving the surface properties, subsequent photochemical treatment with light of a wavelength from 200 to 600 nm.
The invention relates also to a composition comprising
(A) a coating system based on
(I) a polyacrylate polyol and/or polyester polyol with melamine or
(II) a polyacrylate polyol and/or polyester polyol with a blocked or unblocked polyisocyanate or
(III) a carboxyl-, anhydride- or amino-functional polyester and/or polyacrylate with an epoxy-functional polyester or polyacrylate, or
(IV) a mixture of (I), (II), (III) and/or (IV),
(B) an OHxe2x80x94, NH2xe2x80x94, COOHxe2x80x94, epoxy- or NCO-functional resin containing, in addition, at least one ethylenically unsaturated double bond, it being necessary for a spacer group of at least 4 linearly linked atoms to be present between the double bond and the functional group,
wherein components (A) and (B) do not contain halogen, and
(C) at least one photoinitiator.
Constituents of component (A) are, for example, surface-coating or coating-system constituents that are customary in the art. In the context of the present invention, component (A) represents a surface coating or a coating.
Constituents of component (A) are, for example, polymers that are derived from xcex1,xcex2-unsaturated acids or from derivatives thereof. Examples thereof are polyacrylates and polymethacrylates, polymethylmethacrylates impact-resistant modified with butyl acrylate, polyacrylamides and polyacrylonitriles. Also of interest are, for example, silicone acrylates. Further constituents of component (A) may be polyurethanes that are derived on the one hand from polyethers, polyesters and polyacrylates having free hydroxy groups and on the other hand from aliphatic or aromatic polyisocyanates, and precursors thereof. The constituents of component (A) also include, for example, cross-linkable acrylic resins that are derived from substituted acrylic acid esters, for example epoxy acrylates, urethane acrylates or polyester acrylates. Furthermore, alkyd resins, polyester resins and acrylate resins, and modifications thereof, that are cross-linked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates, polyisocyanurates or epoxy resins may be a constituent of component (A).
Component (A) is, for example, generally a film-forming binder based on a thermoplastic or thermocurable resin, predominantly on a thermocurable resin. Examples thereof are alkyd, acrylic, polyester, phenol, melamine, epoxy and polyurethane resins and mixtures thereof. Examples thereof are described, for example, in Ullmann""s Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A18, pp. 368-426, VCH, Weinheim 1991.
Component (A) may be a cold-curable or hot-curable binder, with the addition of a curing catalyst possibly being advantageous. Suitable catalysts that accelerate the full cure of the binder are described, for example, in Ullmann""s Encyclopedia of Industrial Chemistry, Vol. A18, p. 469, VCH Verlagsgesellschaft, Weinheim 1991.
Examples of coatings (A) with specific binders are:
1. surface coatings based on cold- or hot-cross-linkable alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of such resins, where appropriate with the addition of a curing catalyst;
2. two-component polyurethane surface coatings based on hydroxy-group-containing acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
3. one-component polyurethane surface coatings based on blocked isocyanates, isocyanurates or polyisocyanates that are de-blocked during stoving; if desired, the addition of melamine resins is also possible;
4. one-component polyurethane surface coatings based on aliphatic or aromatic urethanes or polyurethanes and hydroxy-group-containing acrylate, polyester or polyether resins;
5. one-component polyurethane surface coatings based on aliphatic or aromatic urethane acrylates or polyurethane acrylates having free amine groups in the urethane structure and melamine resins or polyether resins, where appropriate with the addition of a curing catalyst;
6. two-component surface coatings based on (poly)ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
7. two-component surface coatings based on (poly)ketimines and an unsaturated acrylate resin or a polyacetoacetate resin or a methacrylamidoglycolate methyl ester;
8. two-component surface coatings based on carboxyl-group- or amino-group-containing polyacrylates and polyepoxides;
9. two-component surface coatings based on anhydride-group-containing acrylate resins and a polyhydroxy or polyamino component;
10. two-component surface coatings based on acrylate-containing anhydrides and poly-epoxides;
11. two-component surface coatings based on (poly)oxazolines and anhydride-group-containing acrylate resins or unsaturated acrylate resins or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
12. two-component surface coatings based on unsaturated polyacrylates and polymalonates;
13. thermoplastic polyacrylate surface coatings based on thermoplastic acrylate resins or extrinsically cross-linking acrylate resins in combination with etherified melamine resins;
14. surface-coating systems based on siloxane-modified acrylate resins.
Blocked isocyanates as may be used in component (A) are described, for example, in Organischer Metallschutz: Entwicklung und Anwendung von Beschichtungsstoffen, pp. 159-160, Vincentz Verlag, Hannover (1993). Such compounds are those wherein the highly reactive NCO group is xe2x80x9cblockedxe2x80x9d by reaction with specific radicals, for example, primary alcohols, phenol, ethyl acetoacetate, xcex5-caprolactam, phthalimide, imidazole, oxime and amine. The blocked isocyanate is stable in liquid systems and also in the presence of hydroxy groups. On heating, the blocking agents are removed again and the NCO group is freed.
1-component (1C) and 2-component (2C) systems are described, for example, in Ullmann""s Encyclopedia of Industrial Chemistry, Vol. A18, Paints and Coatings, pp. 404-407, VCH Verlagsgesellschaft mbH, Weinheim (1991).
It is possible to optimise the composition by specially adapting the formulation, for example by varying the binder/cross-linker ratio. The person skilled in the art of surface-coating technology will be familiar with such measures.
In the curing process according to the invention the composition is preferably a composition based on acrylate/melamine, 2-component polyurethane, 1-component polyurethane, 2-component epoxy or 1-component epoxy/carboxy. Mixtures of those systems are also possible, for example the addition of melamine to 1-component polyurethanes.
Component (A) is preferably a binder based on a polyacrylate with melamine. Preference is given also to a system based on a polyacrylate polyol and/or polyester polyol with an unblocked polyisocyanate.
Component (B) consists essentially of monomeric and/or oligomeric compounds having ethylenically unsaturated bonds (pre-polymers) that, in addition, contain at least one or more OH, NH2, COOH, epoxy or NCO groups capable of reacting with the binder and/or cross-linker of component (A). After application and thermal curing, the ethylenically unsaturated bonds are converted into a cross-linked, high-molecular-weight form by means of UV radiation. Examples of component (B) are described, for example, in the publication mentioned hereinbefore, Ullmann""s Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A18, pp. 451-453, or by S. Urano, K. Aoki, N. Tsuboniva and R. Mizuguchi in Progress in Organic Coatings, 20 (1992), 471-486, or by H. Terashima and O. Isozaki in JOCCA 1992 (6), 222. (B) may be, for example, an OH-group-containing, unsaturated acrylate, for example hydroxyethyl acrylate, hydroxybutyl acrylate or a glycidyl acrylate. Component (B) may have any desired structure (for example it may contain units of polyester, polyacrylate, polyether, etc.) provided that it includes an ethylenically unsaturated double bond and also, in addition, free OH, COOH, NH2, epoxy or NCO groups.
(B) may also be obtained, for example, by reacting an epoxy-functional oligomer with acrylic acid or methacrylic acid.
A typical example of an OH-functional oligomer having vinylic double bonds is 
obtained by reaction of CH2xe2x95x90CHCOOH with 
A further possible method of preparing component (B) is, for example, the reaction of an oligomer that contains only one epoxy group and has a free OH group in another position in the molecule.
Also suitable as component (B) are, for example, siloxane-group-containing polymers that contain free OH groups and, in addition, free double bonds. Those polymers can be obtained, for example, by reacting an epoxy-functional polysiloxane with acrylic acid or methacrylic acid or derivatives thereof, for example CH2xe2x95x90CHCOOxe2x80x94CH2CH(OH)CH2Oxe2x80x94(CH2)mxe2x80x94[Si(CH3)2xe2x80x94O]nxe2x80x94Si(CH3)2xe2x80x94(CH2)mxe2x80x94OCH2CH(OH)CH2OC(O)CHxe2x95x90CH2. Such products are available commercially.
Suitable spacer groups of at least 4 linearly linked atoms positioned between the double bond and the functional group in component (B) are, for example, the following structures:
xe2x80x94(CH2)yxe2x80x94, wherein yxe2x89xa74, or 
xe2x80x83wherein yxe2x89xa72, or 
xe2x80x83wherein
x=from 1 to 3 and yxe2x89xa72. Preference is given to 
The number of spacer atoms is at least 4, for example from 4 to 16, 6-16, preferably from 4 to 12.
The compositions contain, for example, from 1 to 50%, e.g. from 5 to 30%, especially from 10 to 25%, component (B), based on 100 parts of component (A).
According to the invention there may be used as photoinitiator (C) any known compound that is capable of initiating radical polymerisation when irradiated with light.
Examples thereof are: benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, for example 1-hydroxy-cyclohexyl-phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one or 2-hydroxy-2-methyl-1-phenyl-propanone, dialkoxyacetophenones, xcex1-hydroxy- or xcex1-amino-acetophenones, for example (4-morpholino-benzoyl)-1-benzyl-1-di-methylamino-propane or (4-methylthiobenzoyl)-1-methyl-1-morpholino-ethane, 4-aroyl-1,3-dioxolanes, benzoin alkyl ethers and benzil ketals, for example 2,2-dimethoxy-1,2-diphenylethan-1-one, monoacylphosphine oxides, for example 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bisacylphosphine oxides, for example bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-(2-methylprop-1-yl)-phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenyl-phosphine oxide and trisacylphosphine oxides. In certain cases it may be advantageous to use mixtures of two or more photoinitiators, for example mixtures of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl-phosphine oxide or bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide with 1-hydroxy-cyclohexyl-phenyl ketone or hydroxy-2-methyl-1-phenyl-propanone or 2-methoxy-1-phenyl-ethane-1,2dione.
Component (C) is preferably a compound of formula I 
wherein
R1 is hydrogen, C1-C18alkyl, C1-C18alkoxy, xe2x80x94OCH2CH2xe2x80x94OR5, a group 
or a group 
wherein
I is an integer from 2 to 10 and
A is a radical 
R2 and R3 are each independently of the other hydrogen, C1-C6alkyl, phenyl, C1-C16alkoxy, OSiR6R7R8 or xe2x80x94O(CH2CH2O)qxe2x80x94C1-C16alkyl wherein
q is an integer from 1 to 20, or
R2 and R3, together with the carbon atom to which they are bonded, form a cyclohexyl ring;
R4 is hydroxy, C1-C16alkoxy or xe2x80x94O(CH2CH2O)qxe2x80x94C1-C16alkyl;
with the proviso that R2, R3 and R4 are not all simultaneously C1-C16alkoxy or xe2x80x94O(CH2CH2O)qxe2x80x94C1-C16alkyl;
R5 is hydrogen, C1-C8alkyl, 
R6, R7 and R8 are each independently of the others C1-C4alkyl or phenyl;
or a compound of formula (Ia) 
wherein
R9, R10, R11 and R12 are each independently of the others hydrogen, methyl, phenyl, methoxy, xe2x80x94COOH, unsubstituted or C1-C4alkyl-substituted phenyl, or a group xe2x80x94OCH2CH2OR5 or xe2x80x94SCH2CH2OR5 wherein
R5 is as defined for formula I;
or a compound of formula (Ib) 
wherein
R13 is hydrogen, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, halogen or a group N(R17)2;
R14 has one of the meanings indicated for R13 or is the group 
in which case the radical R13 from formula Ib and the radical R13 from this group are together a direct bond and the other radicals are as defined below;
R15 is C1-C8alkyl;
R16 is hydrogen, xe2x80x94CHxe2x95x90CHR20, or phenyl that is unsubstituted or mono- to tri-substituted by C1-C12alkyl, C1-C4alkoxy or by halogen; or
R15 and R16, together with the carbon atom to which they are bonded, form a cyclohexyl ring;
R17 and R18 are each independently of the other C1-C4alkyl or
R17 and R18, together with the nitrogen atom to which they are bonded, form a five- or six-membered, saturated or unsaturated ring, which may be interrupted by xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or by xe2x80x94N(CH3)xe2x80x94,
R19 is hydrogen or C1-C12alkyl; and
R20 is hydrogen or C1-C4-alkyl;
or a compound of formula II 
wherein
R21 is naphthyl, anthracyl, an O- or S-containing, 5- or 6-membered heterocyclic ring or a group 
R22 is C1-C12alkyl, cyclohexyl, cyclopentyl, C2-C12alkenyl, phenyl-C1-C4alkyl; phenyl, biphenyl or naphthyl each of which is unsubstituted or mono- to tetra-substituted by C1-C4alkyl and/or by C1-C4alkoxy; C2-C18alkyl interrupted one or more times by xe2x80x94Oxe2x80x94; or Si(R28)(R29)(R30);
R23, R24, R25, R26 and R27 are each independently of the others hydrogen, C1-C8alkyl, C1-C8alkoxy, C1-C8alkylthio, phenyloxy, phenylthio, phenyl that is unsubstituted or mono- to tetra-substituted by C1-C4alkyl and/or by C1-C4alkoxy, phenyl-C1-C4alkyl, halogen or NO2;
R28, R29 and R30 are each independently of the others C1-C8alkyl, cyclohexyl, cyclopentyl, phenyl or C1-C8alkoxy;
or a compound of formula III 
wherein
Z is S or O;
R31 and R32 are each independently of the other C1-C18alkyl, C2-C18alkyl interrupted one or more times by xe2x80x94Oxe2x80x94, phenyl-substituted C1-C4alkyl, C2-C4alkenyl; phenyl, naphthyl or biphenyl each of which is unsubstituted or mono- to penta-substituted by halogen, hydroxy, C1-C8alkyl and/or by C1-C8alkoxy; C5-C12cycloalkyl, an O-, S- or N-containing, 5- or 6-membered heterocyclic ring, or a group COR33, or
R31 is a radical 
OH, OR34, Oxe2x88x92NH4+ or Oxe2x88x92[Mn+]1/n wherein
n is an integer from 1 to 3 and
M is an n-valent metal ion, or
R31 and R32 together are C4-C7alkylene and form a ring together with the P atom to which they are bonded;
R33 is C1-C12alkyl, C3-C12cycloalkyl, C2-C18alkenyl; phenyl, naphthyl or biphenyl each of which is unsubstituted or mono- to tetra-substituted by C1-C8alkyl, C1-C8alkoxy, C1-C8alkylthio and/or by halogen; an O-, S- or N-containing, 5- or 6-membered heterocyclic ring, or a group 
R34 is C1-C8alkyl, phenyl, naphthyl, C1-C8alkylphenyl or C1-C4alkylnaphthyl;
Y is phenylene, C1-C12alkylene or C5-C6cycloalkylene;
X is C1-C18alkylene, C2-C18alkylene interrupted one or more times by xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94NR35xe2x80x94, P(O)R36xe2x80x94 or by xe2x80x94SO2xe2x80x94, or C1-C6alkylene substituted by Cl, F, C1-C4alkoxy, COOR37, phenyl, phenyl-C1-C4alkyl, naphthyl-C1-C4alkyl, C1-C4alkylphenyl, C1-C4alkylnaphthyl, phenyl-C1-C4alkoxy, naphthyl-C1-C4alkoxy and/or by CN, or
X is C1-C8alkylene substituted by one or two radicals of formula A 
or
X is a group of formula A1-A9
wherein
a and b are each independently of the other 0 or 1, and the sum of d and f is an integer from 3 to 8, with the proviso that neither d nor f is 0, or
X is a group xe2x80x94CH2xe2x80x94CHxe2x95x90CHxe2x80x94CH2xe2x80x94 or xe2x80x94CH2xe2x80x94Cxe2x89xa1Cxe2x80x94CH2xe2x80x94, or
X is phenylene, xylyene 
each of which is unsubstituted or mono- to tri-substituted by Cl, F, C1-C4alkyl and/or by C1-C4alkoxy, or
X is phenylene that is substituted by one or two groups (A) and that, in addition, may be mono- to tri-substituted by Cl, F, C1-C4alkyl and/or by C1-C4alkoxy, or
X is a group of formula A10-A13
Q is a single bond, CR39R40, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94NR35xe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94(CH2)pxe2x80x94 or xe2x80x94CHxe2x95x90CHxe2x80x94;
p is an integer from 2 to 12;
Z is O or S;
R35 is hydrogen, C1-C12alkyl or phenyl;
R36 is C1-C4alkyl or phenyl; and
R37 is C1-C12alkyl, C2-C18alkyl interrupted one or more times by xe2x80x94Oxe2x80x94, benzyl, phenyl, cyclopentyl or cyclohexyl;
R38 is hydrogen, C1-C4alkyl, C1-C4alkoxy or halogen;
R38 is hydrogen, methyl or ethyl; and
R40 is hydrogen or C1-C4alkyl;
or component (C) is a mixture of a compound of formula I, Ia, Ib or II with a compound of formula III.
C1-C20Alkyl is linear or branched and is, for example, C1-C18-, C1-C12-, C1-C8-, C1-C6- or C1-C4-alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl-pentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, heptadecyl, octadecyl and icosyl. C1-C18Alkyl, C1-C12alkyl, C1-C8alkyl and C1-C4alkyl are as defined hereinbefore up to the appropriate number of carbon atoms.
C2-C18Alkyl interrupted one or more times by xe2x80x94Oxe2x80x94 or by xe2x80x94Sxe2x80x94 is interrupted, for example, by xe2x80x94Oxe2x80x94 from one to five times, e.g. from one to three times or once or twice, resulting in, for example, structural units such as xe2x80x94S(CH2)2OH, xe2x80x94O(CH2)2OH, xe2x80x94O(CH2)2OCH3, xe2x80x94O(CH2CH2O)2CH2CH3, xe2x80x94CH2xe2x80x94Oxe2x80x94CH3, xe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH2CH3, xe2x80x94[CH2CH2O]yxe2x80x94CH3 wherein y=from 1 to 5, xe2x80x94(CH2CH2O)5CH2CH3, xe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94Oxe2x80x94CH2xe2x80x94CH2CH3 and xe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94Oxe2x80x94CH2xe2x80x94CH3.
C3-C12Cycloalkyl is, for example, cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl. C5-C12Cycloalkyl is, for example, cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl. Preference is given to cyclopentyl and cyclohexyl, especially cyclohexyl.
C1-C18Alkoxy is e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, pentyloxy, hexyloxy, heptyloxy, decyloxy or dodecyloxy, for example C1-C12alkoxy, C1-C8alkoxy, preferably C1-C4alkoxy, especially methoxy. C1-C8Alkoxy is as defined hereinbefore up to the appropriate number of carbon atoms.
C1-C12Alkylthio is linear or branched and is e.g. methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, pentylthio, hexylthio, heptylthio, decylthio or dodecylthio, for example C1-C8alkylthio, preferably C1-C4alkylthio, especially methylthio.
An O- or S-containing, 5- or 6-membered heterocyclic ring is, for example, furyl, thienyl, oxinyl or dioxinyl.
An O-, S- or N-containing, 5- or 6-membered heterocyclic ring is, for example, furyl, thienyl, pyrrolyl, pyridyl, oxinyl or dioxinyl.
C2-C12Alkenyl is, for example, allyl, methallyl, 1,1-dimethylallyl, butenyl, hexenyl, octenyl or dodecenyl, for example C2-C8alkenyl or C2-C4alkenyl, especially allyl. C2-C4Alkenyl is, for example, allyl, methallyl, 1,1-dimethylallyl or butenyl.
The radical xe2x80x94O(CH2CH2O)qxe2x80x94C1-C16alkyl represents from 1 to 20 consecutive ethylene oxide units, the chain thereof being terminated by a C1-C16alkyl. q is preferably from 1 to 10, for example from 1 to 8, especially from 1 to 6. The chain of ethylene oxide units is terminated preferably by a C1-C10alkyl, for example by a C1-C8alkyl, especially by a C1-C4alkyl.
Phenyl-C1-C4alkyl is, for example, benzyl, phenylethyl, xcex1-methylbenzyl or xcex1,xcex1-dimethylbenzyl, especially benzyl.
Substituted phenyl, naphthyl or biphenyl is mono- to penta-, for example, mono- to tetra-, e.g. mono-, di- or tri-, especially di- or tri-substituted.
R31, R32 and R33 as substituted phenyl, naphthyl or biphenyl are substituted, for example, by linear or branched C1-C8alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl or octyl, or by linear or branched C1-C8-alkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy or octyloxy, or by linear or branched C1-C8alkylthio, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio or hexylthio, or by halogen, such as fluorine, chlorine, bromine or iodine. Preferred substituents of R31, R32 and R33 as phenyl, naphthyl and biphenyl are C1-C4alkyl, especially methyl, C1-C4alkoxy, especially methoxy, and chlorine. R31, R32 and R33 are especially, for example, 2,4,6-trimethylphenyl, 2,6-dichlorophenyl, 2,6dimethylphenyl or 2,6-dimethoxyphenyl.
Examples of n-valent metals (n=from 1 to 3) are Na, Li, K, Mg, Ca, Ba, Fe, Co and Al.
When R31, and R32 are C4-C7alkylene and, together with the P atom to which they are bonded, form a ring, that ring (including the P atom) is preferably five- or six-membered.
C1-C8Alkylphenyl is, for example, C1-C4alkylphenyl, for example tolyl, xylyl, mesityl, ethylphenyl or diethylphenyl, preferably tolyl or mesityl. C1-C4Alkylnaphthyl is naphthyl substituted by methyl, ethyl and/or propyl or butyl.
C1-C18alkylene and C1-C12alkylene are linear or branched alkylene, for example methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, tetradecylene, heptadecylene or octadecylene. X and Y are each especially C1-C12alkylene, for example ethylene, decylene, xe2x80x94CH(C11H23)xe2x80x94, xe2x80x94CH(CH3)xe2x80x94CH2xe2x80x94, xe2x80x94CH(CH3)xe2x80x94(CH2)2xe2x80x94, xe2x80x94CH(CH3)xe2x80x94(CH2)3xe2x80x94, xe2x80x94C(CH3)2xe2x80x94CH2xe2x80x94 or 
When X is C2-C18alkylene interrupted by xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94NR35xe2x80x94, xe2x80x94P(O)R36xe2x80x94or by xe2x80x94SO2xe2x80x94, there are obtained, for example, structural units such as xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH2CH2xe2x80x94, xe2x80x94[CH2CH2O]yxe2x80x94 wherein y=from 1 to 9, xe2x80x94(CH2CH2O)7CH2CH2xe2x80x94, xe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94Oxe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94, xe2x80x94CH2xe2x80x94Sxe2x80x94CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94Sxe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2xe2x80x94CH2CH2xe2x80x94Sxe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94(CH2)3xe2x80x94Sxe2x80x94(CH2)3xe2x80x94Sxe2x80x94(CH2)3xe2x80x94, xe2x80x94CH2xe2x80x94(NR35)xe2x80x94CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94(NR35)xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2xe2x80x94(P(O)R36)xe2x80x94CH2xe2x80x94, xe2x80x94CH2CH2xe2x80x94(P(O)R36)xe2x80x94CH2CH2xe2x80x94, 
xe2x80x94CH2xe2x80x94SO2xe2x80x94CH2xe2x80x94 and
xe2x80x94CH2CH2xe2x80x94SO2xe2x80x94CH2CH2xe2x80x94.
C1-C4Alkoxy substituents are, for example, methoxy, ethoxy, propoxy and butoxy, especially methoxy. C1-C6alkylene substituted by C1-C4alkoxy or by xe2x80x94COOR37 is, for example, xe2x80x94CH(OCH3)xe2x80x94 or xe2x80x94CH(COOCH3)xe2x80x94CH2xe2x80x94. C1-C4Alkylphenyl is, for example, tolyl, xylyl, mesityl, ethylphenyl or diethylphenyl, preferably tolyl or mesityl. C1-C4Alkylnaphthyl is naphthyl substituted by methyl, ethyl and/or propyl or butyl. Phenyl-C1-C4alkyl is, for example, benzyl, phenylethyl, xcex1-methylbenzyl or xcex1,xcex1-dimethylbenzyl, especially benzyl. Naphthyl-C1-C4alkyl is, for example, naphthylmethyl, naphthylethyl, naphthyl-(1-methyl)-eth-1-yl or naphthyl-(1,1-dimethyl)eth-1-yl, especially naphthylmethyl. Phenyl-C1-C4alkoxy is to be understood as being, for example, benzyloxy, phenylethyloxy, xcex1-methylbenzyloxy or xcex1,xcex1-dimethylbenzyloxy, especially benzyloxy. Naphthyl-C1-C4alkoxy is, for example, naphthylmethyloxy or naphthylethyloxy.
Examples of groups of formula (A1) wherein the sum of d and f is from 3 to 8 are: 
Preference is given to 
Examples of groups of formulae A2, A3, A4, A5, A6, A7, A8 and A9 are 
Examples of groups of formula A10 are 
Examples of unsubstituted and substituted phenylene and xylylene are 
The preparation of compounds of formulae I and Ia is generally known and some of the compounds are available commercially. The preparation of oligomeric compounds of formula I is described, for example, in EP-A-161 463. A description of the preparation of compounds of formula Ia may be found, for example, in EP-A-209 831.
The preparation of compounds of formula Ib is described, for example, in EP-A-284 561. The compounds of formula III are prepared, for example, in the manner disclosed in EP-A-184 095. Some compounds of formulae Ib, II and III are also available commercially.
Preference is given to compounds of formula I wherein R1 is hydrogen, C1-C12alkyl or xe2x80x94OCH2CH2xe2x80x94OR5; R2 and R3 are each independently of the other C1-C6alkyl, phenyl or C1-C16alkoxy or R2 and R3, together with the carbon atom to which they are bonded, form a cyclohexyl ring; R4 is hydroxy or C1-C16alkoxy; R5 is hydrogen or 
and to compounds of formula (Ia) wherein R9, R10, R11 and R12 are hydrogen; and to compounds of formula (Ib) wherein R13 is hydrogen; R14 is C1-C4alkylthio or N(R17R18); R15 is C1-C8alkyl; R16 is phenyl; R17 and R18 are each independently of the other C1-C4alkyl or R17 and R18, together with the nitrogen atom to which they are bonded, form a saturated six-membered ring, which may be interrupted by xe2x80x94Oxe2x80x94; and to compounds of formula II wherein R21 is phenyl and R22 is C1-C12alkyl; and to compounds of formula III wherein Z is O; R31 and R32 are each independently of the other C1-C18alkyl; phenyl that is unsubstituted or mono- to penta-substituted by C1-C8alkyl and/or by C1-C8-alkoxy; or a group COR33; and R33 is phenyl that is unsubstituted or mono- to tetra-substituted by C1-C8alkyl or by C1-C8alkoxy.
Preferably, R2 and R3 in formula I are each independently of the other C1-C6alkyl or, together with the carbon atom to which they are bonded, form a cyclohexyl ring, and R4 is hydroxy.
More especially, R2 and R3 in formula I are identical and are each methyl, and R4 is hydroxy or isopropoxy.
In formula Ia R9-R12 are preferably hydrogen.
Preferably, R16 in formula Ib is phenyl or xe2x80x94CHxe2x95x90CHR20, R14 is C1-C4alkylthio or N(R17)2, and R15, R17 and R18 are C1-C4alkyl.
In formula II R21 is preferably phenyl and R22 is C1-C4alkyl.
Preferably, R31 in formula III is COR33 wherein R33 is phenyl mono- to tetra-substituted by C1-C4alkyl, C1-C4alkoxy and/or by halogen, and R32 is C1-C12alkyl, unsubstituted phenyl or phenyl mono- to penta-substituted by C1-C4alkyl and/or by C1-C4alkoxy.
Furthermore, in formula III preferably R31 and R32 are phenyl and R33 is phenyl mono- to tri-substituted by C1-C4alkyl and/or by C1-C4alkoxy.
Z is preferably O.
As component (C) special preference is given to 1-hydroxy-cyclohexyl-phenyl ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one or 2-hydroxy-2-methyl-1-phenyl-propanone, (4-morpholino-benzoyl)-1-benzyl-1-dimethylamino-propane or (4-methylthiobenzoyl)-1-methyl-1-morpholino-ethane, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,6-dimethoxybenzoyl-2,4,4-trimethylpentyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-(2-methylprop-1-yl)-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide, and mixtures of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl-phosphine oxide with 1-hydroxy-cyclohexyl-phenyl ketone, hydroxy-2-methyl-1-phenyl-propanone or 2-methoxy-1-phenyl-ethane-1,2-dione; or of bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide with 1-hydroxy-cyclohexyl-phenyl ketone, hydroxy-2-methyl-1-phenyl-propanone or 2-methoxy-1-phenyl-ethane-1,2-dione; or of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide with 1-hydroxy-cyclohexyl-phenyl ketone, hydroxy-2-methyl-1-phenyl-propanone or 2-methoxy-1-phenyl-ethane-1,2-dione.
The photopolymerisable compositions contain the photoinitiator (C) advantageously in an amount from 0.05 to 20% by weight, preferably from 2 to 10% by weight, based on 100 parts of component (A).
When the photoinitiator (C) is a mixture of a compound of formula I, Ia, Ib or II with a compound of formula III, the proportion of the compound(s) of formula I, Ia, Ib or II in the mixture is, for example, from 25 to 90%, e.g. from 25 to 75%, preferably from 50 to 75%.
Preference is given to a composition comprising (A) polyester polyol, acrylate polyol or hexamethoxymethylmelamine and (B) isocyanurate or OH-functionalised acrylate and (C) 1-hydroxy-cyclohexyl-phenyl ketone or 25% bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl-phosphine oxide and 75% 1-hydroxy-cyclohexyl-phenyl ketone or 4-[(2-hydroxyethoxy)-benzoyl]-1-hydroxy-1-methyl-ethane.
It is characteristic of the composition that it comprises an OHxe2x80x94, NH2xe2x80x94, COOHxe2x80x94, epoxy- or NCO-functionalised component that also, in addition, contains free double bonds separated from the functional group by a spacer group of at least 4 linearly linked atoms (B), and a photoinitiator (C). In accordance with the process according to the invention, the addition of those components allows a further cross-linking of the surface coating on irradiation with light after the thermal curing, resulting in a surface coating having improved surface properties, especially in respect of the hardness and resistance to scratching.
The surface coatings according to the invention may comprise an organic solvent or solvent mixture in which the binder and/or the cross-linker is (are) soluble or dispersible. The composition may, however, also be an aqueous solution or dispersion. It is also possible, for example, for one of the two components to serve as the dispersion medium or dissolution medium for the other component. The vehicle may also be a mixture of an organic solvent and water. The coating may also be a high-solids surface coating or may be solvent-free (for example, powder coating composition).
The compositions according to the invention are prepared by mixing all the components. It is also possible, for example, first to link only the OHxe2x80x94, NH2xe2x80x94, COOHxe2x80x94, epoxy- or NCO-functionalised component (B) with component (A), or with a constituent thereof, via the functional group in question, and thereafter to mix in all the other constituents.
The compositions according to the invention may be applied to any desired substrates, for example to metal, wood, plastics or ceramic materials. They are preferably used as finishing lacquers for the surface-coating of motor vehicles. When the finishing lacquer consists of two layers the lower layer of which is pigmented and the upper layer of which is not pigmented, the coating according to the invention may be used for the upper or the lower layer or for both layers, but preferably for the upper layer.
The compositions according to the invention may be applied to the substrates in accordance with the customary procedures, for example by painting, spraying, pouring, immersion or electrophoresis; see also Ullmann""s Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A18, pp. 491-500.
The invention therefore relates also to a process for the coating of a substrate wherein a composition according to the invention is applied to the surface of the substrate, cured by means of heating and then irradiated with UV light.
In addition to the photoinitiator the compositions may comprise further customary additives, or it is possible to add further additives to the formulation in the process according to the invention. For example, the composition may comprise further components in addition to components. (A), (B) and (C), or in the process according to the invention it is possible to add to components (B) and (C) further additives, for example light stabilisers, solvents, pigments, dyes, plasticisers, stabilisers, thixotropic agents, drying catalysts and/or flow improvers. Possible components are, for example, such as are described in Ullmann""s Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A18, pp. 429-471, VCH, Weinheim 1991.
UV-absorbers, for example those of the hydroxyphenyl-benzotriazole, hydroxyphenyl-benzophenone, oxalic acid amide or hydroxyphenyl-s-triazine type, may be added as light stabilisers. There may be used, for example, individual compounds or mixtures of those compounds with or without the use of sterically hindered amines (HALS).
Possible drying catalysts, or curing catalysts, are, for example, organic metal compounds, amines, amino-group-containing resins and/or phosphines. Organic metal compounds are, for example, metal carboxylates, especially those of the metals Pb, Mn, Co, Zn, Zr and Cu, and metal chelates, especially those of the metals Al, Ti and Zr, and organometal compounds, for example organotin compounds. Examples of metal carboxylates are the stearates of Pb, Mn and Zn, the octanoates of Co, Zn and Cu, the naphthenates of Mn and Co and the corresponding linoleates, resinates and tallates.
Examples of metal chelates are the aluminium, titanium and zirconium chelates of acetyl-acetone, ethyl acetoacetate, salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone and ethyltrifluoroacetoacetate and the alcoholates of those metals. Examples of organotin compounds are dibutyltin oxide, dibutyltin dilaurate and dibutyltin dioctanoate. Examples of amines are especially tertiary amines, for example tributylamine, triethanolamine, N-methyl-diethanolamine, N-dimethylethanolamine, N-ethylmorpholine, N-methyl-morpholine and diazabicyclooctane (triethylenediamine) and salts thereof. Further examples are quaternary ammonium salts, for example trimethylbenzylammonium chloride. Amino-group-containing resins act simultaneously as binder and curing catalyst. Amino-group-containing acrylate copolymers are examples thereof. As curing catalyst there may also be used phosphines, for example triphenyl-phosphine. The pigments may be inorganic, organic or metallic pigments. Preferably, the coatings according to the invention contain no pigments and are used as clear lacquer.
Preference is given to the use of the composition according to the invention as a coating, especially as a finishing lacquer for use in the furniture industry and automobile industry, more especially as a pigmented or non-pigmented top layer of the surface coating. The use thereof for underlying layers is, however, also possible. When the composition according to the invention is used in the underlying layer, with the simultaneous use of a UV-curable finishing lacquer, the adhesion of the UV-curable finishing lacquer to the underlying layer is improved as a result of the reaction of the double bonds present in each of the layers.
Preference is given to non-pigmented compositions and to a curing process without the addition of pigments.
The curing of the compositions according to the invention is carried out thermally at first. The surface is after-cured by subsequent irradiation with UV light. Accordingly, in the curing process according to the invention, the coating to be cross-linked is first of all cured by the action of heat and the surface hardness is improved by the subsequent irradiation with UV light.
The thermal curing is carried out generally in an oven, for example a circulating-air oven, or by means of irradiation with IR lamps. Curing at room temperature without aids is likewise possible, depending on the binder system used. The curing temperatures are generally from room temperature to 150xc2x0 C., for example from 25 to 150xc2x0 C. or from 50 to 150xc2x0 C. In the case of powder coating compositions, the curing temperatures may be even higher, for example up to 250xc2x0 C.
The photochemical curing step is carried out, usually using light of wavelengths from about 200 nm to about 600 nm, especially from 200 to 450 nm. As light sources there are used a large number of the most varied types. Both point sources and planiform projectors (lamp carpets) are suitable. Examples are: carbon arc lamps, xenon arc lamps, medium-, high- and low-pressure mercury lamps, optionally doped with metal halides (metal halide lamps), microwave-excited metal-vapour lamps, excimer lamps, superactinic fluorescent tubes, fluorescent lamps, argon filament lamps, electronic flash lamps, photographic flood lights, electron beams and X-rays generated by means of synchrotrons or laser plasma. The distance between the lamp and the substrate according to the invention to be irradiated may vary, for example, from 2 cm to 150 cm, according to the intended use and the type and strength of the lamp. Laser-light sources, for example excimer lasers, are especially suitable. The selection of the type of lamp is dependent especially on the type of photoinitiator (C) used. For example, bisacylphosphine oxide photoinitiators are excited even by lamps having an emission spectrum of relatively long wavelength.